Process of obtaining carbon black and alpha gaseous mixture of hydrogen and nitrogenin controlled proportions by the thermal dissociation of hydrocarbon gases and vapors



Oct. 10, 1933. w 11 w|Lcox 1,929,664

PROCESS OF osmmme CARBON BLACK AND A GASEOUS MIXTURE OF nvnnoenm AND mwnoerm IN CONTROLLED PROPORTIONS BY THE THERMAL mssocIA'rlon OF HYDROCARBON GASES AND VAPORS Filed June 28, 1930 ATTORNEY.

Patented Oct. '10, 1933 1,929,664 v UNITED STATES PATENT OFFICE PROCESS OF OBTAINING CARBON BLACK AND A GASEOUS MIXTURE OF HYDRO- GEN AND NITROGEN IN CONTROLLED PROPORTIONS BY THE THERMAL DIS- SOCIATION OF HYDROCARBON GASES AND VAPORS William D. Wilcox, Lawrence, Kans. Application June 28, 1930. Serial No. 464,691 8 claims. (01. 23-1) Numerous patents have been issued covering carbon; G, is an oil absorption scrubber which plant and process for the recovery of carbon may be used for the recovery of condensible and/or hydrogen by the thermal dissociation of polymerization products; H, is the chamber in hydrocarbon gases or vapors, derived from oil. In which final dissociation is effected.

some, external heating is employed; in others, I do not limit myself in the operation of the 55 the hydrocarbons are passed in contact with inprocess to the use of any particular means of candescent coke or with checker brick brought to cooling the gas and removing the entrained cara high temperature by precedent blasting. In bon. F and G may not be needed and I may use none so far as I have been able to ascertain has other forms of plant commonly known and used there been obtained along with recovery of carfor the removal of liquid hydrocarbons. e What is 0 bon, a mixture of the hydrogen residue with new in my process will be found in A, B, C and H. nitrogen from the air freed from its oxygen, in the Means are provided for maintaining an active proportions required for use of the mixture in the combustion in the base of A by the admission of synthesis of ammonia, nor has dissociation actualfuel gas through 9-9 from 8, and air through 1y been carried to the completion necessary. to 6-6 from 3 into burners 1010. The combustion '65 give freedom from the presence in the mixture gases'pass up A, and down 13, thence through 4 of undecomposed hydrocarbons. into C and to the air. Air under pressure ad- In one, at least, the value of the hydrogen for mitted through 1 passes down through 2 into 3, the special purpose for which it was produced, Simultaneously gas through 9 air h o h 5 has justified such a long time of contact as permay be admitted to 11, passed up through B and 70 mitted a reduction of the hydrocarbons to less down through 12 in A, thence through 13, D, E, F than 5%, but so long-a time of contact would not, and G, for the removal of carbon and products of generally speaking, be commercially practicable. thermal dissociation other than gas. In H, valve Many have named temperatures above that at controlled pipe 19, admits gas, valve controlled which, equilibrium being established, the percent pipe 21 admits steam to manifold pipe 20, 24 75 of hydrocarbons present would be negligible, but is a system of pipes in H conveying gas to vertimore often than otherwise, the means provided cal conduit 26. Valve controlled pipe 22 conveys for creating and maintaining these temperatures air from 3 to manifold pipe 23, conveying air has been inadequate. Nor has there been comthrough system of pipes 25 to vertical conduit 2'7,

plete successinthe recovery of the carbon. Much 28 indicates openings admitting gas and air to 0 the larger portion has remained within the disthe base of combustion chamber 29, 30 are outlet sociation zone and not recovered, or if later repipes for the product withdrawn from H. moved by mechanical means, has been so sintered Heating is by external means, the attainment together by long exposure to heat, that the fineof an adequate temperature being facilitated by .35 ness of subdivision which is its chief element of the use of air preheated in a heat exchange with 5 value, has been greatly impaired. The process the combustion gases, to .support the burning of is preferably carried out either in a single unit combustible Active combustion is in the or in a multi-stage procedure in plant such as lower portion of whatIcall the dissociation chamshown by the accompanying drawing which is her A. The hot gases pass up through the dissofiled and made a part of these specifications, but ciation chamber, down through adjacent pre- 0 the essential features of the process may be carheating chambers B and B and into the heat exried out in plant departing in many details from change C. The travel of the gases which it is that of the preferred'form shown by the drawing, sought to dissociate is counter current to the In the drawing, A may be called the dissociatravel of the heating gases. The gases to be tion' chamber; B, the preheating chamber; C, a dissociated are passed through tubes or conduits 5 heat exchange chamber; D, shows means of preferably of heat resisting alloy except that in ducing the temperature of the hot gas passing in the zone of highest heat, refractory materials through 13; E, is an electric precipitator; F, a may be substituted in the walls of'the conduit. I scrubber which may be used for further cooling find that increase of carbon recovered may be and cleaning the gas following removal of the ,effected by increasing the height of the conduit required time or heating may be given to the gas and ot the some time o higher velocity than has been employed in the post. I find as further gain in preventing edherence or the corbon to the inner surfaces or the conduit by me tsinihg on excess of pressure the mein pipe supplying gas, so that the velocity oi trovel oi the one may be increased periodically 'Zor brief in terveh. Tins may appear 2. very obvious means or efiectlng the result stated, but .lelo not rind that it has ever been employed or proposed prior tomy use or Following passage through the messciotmn Zone, the gas may be cooled and the carbon re= moved by well-known The entire process assume the gas treated to be a pure methane. 5

cu. ft. oi CH4 ore united with 5 cu. it. of air. The r e a c t i o n. s may be represented by the e o u o t lo n dCl-l-l-Oz-l-tllz-i-hect equols 3C+2CO+l0Hz+llzc There is generated by the union C+.0 -CO, to B. t. 11. per cu. it. in excess oi that required to efiect the dissociation of the Cfiimolecule, but us the dissociation of each cu.

it. of CH4 to EH-2H2 which absorbs around E. t; u. per curt, e substantial eddition or host must be supplied from the combustion gases, through the wells or the conduit in order that the temperature or the hydrocarbon gases be mointsined end the reactions proceed rapidly and to completion. Because of the dimculty of msin= 'teining the necesssry high temperature, but

stage procedure the temperature of the second chiefly in order to obtoin a better quality of corbon, I may elect to carry out dissociotion without the addition of air and to complete it in o two= unit being much higher than is maintained in the first, removing the carbon by means immediately following the issuance of the gases from the dissociation zone of each.

Assuming a dissociation of approximately 90% to have been attained, 10 cu. ft. of CH4 has become 1 cu. ft. CH4 and 18 cu. ft. of Hz. This mixture is conveyed into the dissociation unit shown in vertical cross section in Fig. 3. This unit is heated initially by internal combustion so that air and gas, admitted in determined volume through separate inlets and conveyed through a preheating zone, are brought to temperatures much in excess of that at which the oxygen of .a volume of air inadequate to form an explosive mixture will unite with the gas upon mixture taking place. I find the temperature required to bring about this union of the oxygen in the air with the combustible of the gas to be in the neighborhood of 1300" F. This procedure may be carried out in plantdiflering materially in design from that sbown by the drawing and I do not limit myself in carrying out this final step of the temperature of the gaseous current in contact with the exterior of the conmorocco in which-dissociation telres place, so that the externnlly hosted conduit, shown in Fig. 3;, prior to its union with air by adding at small proportion. of steam to the gas. This is by no means essential to the result sought but will be good proctice. 55

Let us assume the gases end air heated to ltllilfi We add to the gas sir us indicated by the fol lowing:

lCHl+ltHr+l.50i+oNz. This following combination will equal Knowing the composition of the the degree of dissociation, the gas and air readily be proportioned so so to approximate the volumetric ratio or hydrogen end nitrogen desired. t'J-}-=CO generates 3t 3. u. cu. ft. in addition to the bent required to dis= sociste the molecule or CH4. H4+Os=2HrO gen= eretes 548 B. t. u. net 2 cu. ft. oi hydrogen be W consumed. Adding the hest so generetecl to s gaseous mixture clreody preheated to loot El, and o temperature less than eooo F. only by res-son or the increased specific host of gsses at high temperatures will result. This is o tempereture which it would be difllcult to create by external means or to import for more then s brier operating interval by contact with surfaces brought to high temperature by precedent blush ing. The highly heated mixture passes out counter current and in contact with the exterior surfaces of the pipes which are bringing in the unheated air and gee, and is fully adequate to bring them to the desired temperature or preheet prior to their passage into the chumber where they are brought together. The rmotions taking place within the dissccintion unit supply the high temperature necesseryto on sociote the remeining hydrocarbons. it eppesrs quite clear that by reason of themuch higher mixture which results from the procedure described then-hes been employed in the past or stipulated in prior issued patents directed to the accomplishment of the complete dissociation of hydrocarbon gases, and by reason of the greater efilnity for carbon than for hydrogen which is displayed by oxygen at high temperatures, the residue 0! hydrocarbons in the gas following its unionwith the air, will be completely decomposed. The addition of steam to the gas prior to its passage through H will be round to accelerate dissociation. This may be introduced in the way shown in the lllill drawin or may be very conveniently added by a. water spray employed to cool the gas in place of the external cooling effected in D. Means of removingthe oxides of carbon and of further purifying the gaseous mixture issuing from 30'--30 are well known and need not be described.

What I claim as new and desire to protect by a. partial dissociation of hydrocarbon gases by passing them through the interior or a conduit, heated to progressively higher temperatures by the'contact of combustion gases, flowing counter duit. partially cooling the gases issuing. fromv the conduit, and removing the entrained carbon theretrom,adding steam to\t he gas and passing it through an externally heated onduit, thereby bringing it to a temperature ingxcess of 1300- F., simultaneously passing a controlled propormixture of hydrogen and nitrogen in controlled proportions, which comprises simultaneously preheating a volume of hydrocarbon gases and a closely proportioned volume of air less than suf- ',flcient to form an explosive mixture to an ignition temperature, by passing them through conduits heated by the passage of hot combustion gases passed counter current to the direction of travel of the gas'and air, in contact with the exterior surfaces of the conduits, bringing the gas and air so preheated into admixture in a conduit heated toa temperature at which a substantially complete dissociation of the hydrocarbons will be effected, cooling the gases, removing the entrained carbon therefrom, and eliminating the oxides of carbon from the mixture of gases.

3. The process of obtaining carbon-black and a mixture of hydrogen and nitrogen in controlled proportions by the dissociation of hydrocarbon gases and vapors, which comprises heating a conduit to a dissociation temperature by the contact of combustion gases passed from one extremity of the conduit to a discharge outlet at the other extremity, simultaneously passing hydrocarbon gases through the conduit in a direction reverse to the travel of the combustion gases, so controlling the temperature and length of travel as to secure dissociation at a velocity of travel of the hydrocarbon gases through the-conduit as substantially overcomes the tendency of the evolved carbon to adhere to the interior walls of the conduit, removing the carbon' entrained in the gas issuing from the conduit, then passing the gas through a conduit enclosed in a heating chamber, bringing it to a temperature in excess of l8 00 F., simultaneously passing a volume of air in such relation to the volume of gas as will supply the desired pro-. portion of nitrogen in the conserved product through a conduit within the heating chamber and bringing it to a temperature in. excess of 1800 F., uniting the gas and air within a combustion chamber and withdrawing the product gas through the heating chamber in contact with the exterior surfaces of the enclosed conduit and in counter current flow with the travel of the gas and air, withdrawing the product gas and removing the oxides of carbon therefrom.

4. The process of obtaining carbon black and a mixture of hydrogen and nitrogen in controlled proportions, which comprises passing hydrocarbon gases through a conduit heated by external means to a temperature at which dissociation of the hydrocarbon gases will be substantially complete, concurrently admitting air in a volume less than sufiicient to form an explosive mixture and in volume suflicient to supply to the product the proportion of nitrogen desired at an in grmediate point 'in the travel of the gas through the conduit, withdrawing the resultant trained carbon, removing the exterior surfaces 'ing it to a temperature in product gas, cooling it and removin the enthe oxides of carbon from the gas.

5. The steps in the process of obtaining carbon black and a mixture of hydrogen and nitrogen in controlled proportions by the dissociation of hydrocarbon gases and vapors, following a partial dissociation of the hydrocarbon gases by heating them to a dissociating temperature in the absence of air or steam, and the removal of the evolved carbon from the gas, which comprises adding a small proportion of steam to the gas and passing it through a conduit enclosed in a heating chamber, and bring it to a temperature in excess of 1800F., concurrently passing a relation to the volume of gas as to supply the desired proportion of nitrogen through a conduit enclosed in the heating chamber, and bringing it .to a temperature in excess of 1800 F., uniting the gas and air in a combustion chamber and withdrawing the product gas through the heating chamber in contact with the exterior surfaces of the conduit therein.

6. Theprocess of obtaining carbon black and a mixture of hydrogen and nitrogen in controlled proportions, which comprises passing hydrocarbon gases and vapors through a conduit brought to a dissociation temperature by external combustion, partially cooling the product gas and removing the entrained carbon, thereafterheatexcess of 1300 F.. simultaneously heating a volume of air less than sufficient to form an explosive mixture and in such proportion relative to the volume of gas as to supply the proportion of nitrogen desired to a temperature in excess of 1300 F., uniting the gas and air in a combustion chamber, withdrawing the product gas and removing the oxides of carbon.

'7. The process of obtaining carbon black and a mixture of hydrogen and nitrogen in controlled proportions, which comprises adding to a volume of hydrocarbon gas a volume of air less than suflicient to form an explosive mixture and in sufllcient volume to supply the desired proportion of nitrogen, passing the mixture through a conduit placed within an enclosing combustion chamber, the interior surfaces of which are heated to a temperature at which a substantially complete dissociation is effected, withdrawing the product gas, removing the entrained carbon and thereafter removing the oxides of carbon.

8. The improvement in the process of obtaining carbon black, together with a mixture of hydrogen and nitrogen in controlled proportions byv the passage of hydrocarbon gases through a conduit, heated by external means, to a dissociating temperature, whichcomprises adding to the hydrocarbon gases prior to subjecting them to a dissociating temperature within the conduit, a volume of air less than suflicient to form an exposive mixture and so proportioned relative to the volume of hydrocarbon gases as to volume of air to proportioned supply the desired proportion of nitrogen in the product gas.

' WILLIAM D. WILCOX. 

